CN102334225B - Solid sulfide electrolyte material - Google Patents

Solid sulfide electrolyte material Download PDF

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Publication number
CN102334225B
CN102334225B CN201080009590.4A CN201080009590A CN102334225B CN 102334225 B CN102334225 B CN 102334225B CN 201080009590 A CN201080009590 A CN 201080009590A CN 102334225 B CN102334225 B CN 102334225B
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solid electrolyte
electrolyte material
sulfide solid
sulfide
active material
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CN102334225A (en
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辰己砂昌弘
林晃敏
滨重规
川本浩二
土田靖
长濑浩
上野幸义
神谷正人
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Toyota Motor Corp
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Toyota Motor Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/22—Alkali metal sulfides or polysulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G17/00—Compounds of germanium
    • C01G17/006—Compounds containing, besides germanium, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/002—Inorganic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Abstract

Disclosed is a solid sulfide electrolyte material which generates a slight amount of hydrogen sulfide. Specifically disclosed is a solid sulfide electrolyte material which is characterized by being produced from a raw material composition comprising Li2S and a sulfide of a Group 14 or 15 element and substantially not containing crosslinked sulfur and Li2S.

Description

Sulfide solid electrolyte material
Technical field
The present invention relates to the sulfide solid electrolyte material that hydrogen sulfide generation is few.
background technology
In recent years, fast universal along with information association equipment and communication equipments etc. such as PC, video camera and mobile phones, the exploitation of the battery be utilized as its power supply more and more comes into one's own.In addition, in automobile industry field etc., carrying out height that is used for electric vehicle or Hybrid Vehicle and exporting and the exploitation of the battery of high power capacity.At present, in various battery, high from the view point of energy density, lithium battery gets most of the attention.
Commercially available at present lithium battery uses the electrolyte containing flammable organic solvent, therefore, when needing to carry out suppressing short circuit the safety device that temperature rises installation and for preventing the improvement of the structure/material aspect of short circuit.
For this situation, electrolyte is become solid electrolyte layer thus makes the lithium battery of battery total solids, owing to not using flammable organic solvent in battery, therefore, the simplification achieving safety device can be thought, and manufacturing cost and productivity ratio excellent.In addition, as the solid electrolyte material for such solid electrolyte layer, known sulfide solid electrolyte material.
Sulfide solid electrolyte material is high due to Li ionic conductivity, therefore, is realizing in the high output of battery useful, is carrying out various research all the time.Such as, in patent documentation 1, disclose main component by Li 2(X is SiS to S-X 2, GeS 2, P 2s 5, B 2s 3) manufacture method of the glass sulfide solid electrolyte material that forms and the sulfide solid electrolyte material that utilizes melting and sharp cooling.In addition, the 0.6Li utilizing melting and sharp cooling to manufacture is disclosed in the embodiment of patent documentation 1 2s-0.4SiS 2be sulfide solid electrolyte material, 0.6Li 2s-0.4GeS 2it is sulfide solid electrolyte material etc.In addition, Patent Document 2 discloses the Li that use is synthesized under given conditions 2s is as the Li of raw material 2s-SiS 2it is vitreous solid electrolyte.In addition, the 60Li utilizing melting and sharp cooling to manufacture is disclosed in the embodiment of patent documentation 2 2s-40SiS 2be sulfide solid electrolyte material, 63Li 2s-36SiS 2-1Li 3pO 4it is sulfide solid electrolyte material etc.
On the other hand, Patent Document 3 discloses existence with Li 2s and P 2s 5for the glassy phase of main component and the sulfide based crystallized glass of crystalline phase.In addition, Patent Document 4 discloses the Li in X-ray diffraction with specific diffraction maximum 2s-P 2s 5based crystallized glass.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 6-279050 publication
Patent documentation 2: No. 3510420th, Japan Patent
Patent documentation 3: Japanese Unexamined Patent Publication 2002-109955 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2005-228570 publication
Summary of the invention
Invent problem to be solved
, there is the problem producing a large amount of hydrogen sulfide when contacting with water (containing moisture, identical below) in sulfide solid electrolyte material in the past.In view of the above problems, main purpose of the present invention is, provides the sulfide solid electrolyte material that hydrogen sulfide generation is few.
For the method for dealing with problems
In order to solve the problem, in the present invention, provide a kind of sulfide solid electrolyte material, use containing Li 2the feedstock composition of the sulfide of S and IV main group or V major element forms, and it is characterized in that, in fact not containing crosslinked sulphur and Li 2s.
According to the present invention, sulfide solid electrolyte material is not in fact containing crosslinked sulphur and Li 2s, therefore, it is possible to form the few sulfide solid electrolyte material of hydrogen sulfide generation.
In foregoing invention, described sulfide solid electrolyte material is preferably chalcogenide glass.Thising is presumably because: chalcogenide glass is more soft compared with crystallization chalcogenide glass, therefore, such as, when making solid state battery, the dilation of active material can be absorbed, cell excellent in cycle characteristics.
In foregoing invention, the peak of described crosslinked sulphur do not detected preferably by raman spectroscopy, measured by X-ray diffraction and described Li do not detected 2the peak of S.
In foregoing invention, above-mentioned IV main group or V major element are preferably P, Si or Ge.This is because the lower sulfide solid electrolyte material of hydrogen sulfide generation can be obtained.
In foregoing invention, preferred described feedstock composition is only containing Li 2s and P 2s 5, and the Li contained in described feedstock composition 2the molar percentage of S is in the scope of 70% ~ 85%.This is because, pass through Li 2the range set of the molar percentage of S is comprise just being formed the value (75%) of (オ ル ト Group becomes) and the scope of approximation thereof, can reduce hydrogen sulfide generation further.
In foregoing invention, preferred described feedstock composition is only containing Li 2s and SiS 2, or only containing Li 2s and GeS 2, and the Li contained in described feedstock composition 2the molar percentage of S is in the scope of 50% ~ 80%.This is because, pass through Li 2the range set of the molar percentage of S is the value (66.7%) and approximation thereof that are just being formed, can reduce hydrogen sulfide generation further.
In addition, in the present invention, provide a kind of sulfide solid electrolyte material, by only Li will be contained 2s and P 2s 5feedstock composition amorphization and obtain, it is characterized in that, the Li in described feedstock composition 2the molar percentage of S is in the scope of 70% ~ 85%.
According to the present invention, by making the Li in feedstock composition 2the molar percentage of S is predetermined scope, can obtain the sulfide solid electrolyte material that hydrogen sulfide generation is few.
In addition, a kind of lithium battery is provided in the present invention, have: the positive electrode active material layer containing positive active material, negative electrode active material layer containing negative electrode active material and the dielectric substrate formed between described positive electrode active material layer and described negative electrode active material layer, it is characterized in that, at least one layer in described positive electrode active material layer, described negative electrode active material layer and described dielectric substrate is containing above-mentioned sulfide solid electrolyte material.
According to the present invention, by using above-mentioned sulfide solid electrolyte material, the lithium battery that hydrogen sulfide generation is few can be obtained.
In addition, provide a kind of manufacture method of sulfide solid electrolyte material, it is characterized in that, have: preparation section in the present invention, preparation is containing Li 2the feedstock composition of S and the sulfide containing IV main group or V major element; With amorphization operation, make described feedstock composition amorphization by amorphization process, and described feedstock composition is can obtain in fact not containing crosslinked sulphur and Li 2the ratio of the sulfide solid electrolyte material of S, containing described Li 2s and the sulfide containing IV main group or V major element.
According to the present invention, feedstock composition contains Li with predetermined ratio 2s and the sulfide containing IV main group or V major element, therefore, it is possible to obtain the few sulfide solid electrolyte material of hydrogen sulfide generation.
In foregoing invention, preferred described feedstock composition is only containing Li 2s and P 2s 5, and the Li contained in described feedstock composition 2the molar percentage of S is in the scope of 70% ~ 85%.This is because, pass through Li 2the range set of the molar percentage of S is the scope comprising value (75%) and the approximation thereof just formed, and can reduce hydrogen sulfide generation further.
In foregoing invention, above-mentioned amorphization process is preferably mechanical lapping.This is because, can process at normal temperatures, thus the simplification of manufacturing process can be realized.
Invention effect
In the present invention, even if sulfide solid electrolyte material is when contacting with water, also play the effect that hydrogen sulfide can be suppressed to produce.
Accompanying drawing explanation
Fig. 1 is the schematic section of an example of the generating element representing lithium battery of the present invention.
Fig. 2 is the key diagram of an example of the manufacture method that sulfide solid electrolyte material of the present invention is described.
The result of the raman spectroscopy of the sulfide solid electrolyte material that Fig. 3 is embodiment 1-1 ~ 1-3, obtain in comparative example 1-2,1-3.
The result that Fig. 4 is embodiment 1-1,1-2, the X-ray diffraction of sulfide solid electrolyte material that obtains in comparative example 1-2,1-4 measure.
The hydrogen sulfide generation of the sulfide solid electrolyte material that Fig. 5 is embodiment 1-1 ~ 1-3, obtain in comparative example 1-1 ~ 1-4 measures the result of (particle).
The hydrogen sulfide generation of the sulfide solid electrolyte material that Fig. 6 is embodiment 1-2, obtain in comparative example 1-5 measures the result of (battery).
Fig. 7 is embodiment 2-1,2-2, the hydrogen sulfide generation of sulfide solid electrolyte material that obtains in comparative example 2-1,2-2 measure the result of (particle).
The hydrogen sulfide generation of the sulfide solid electrolyte material that Fig. 8 is embodiment 3-1 ~ 3-3, obtain in comparative example 3-1,3-2 measures the result of (particle).
Fig. 9 is the result of hydrogen sulfide generation mensuration (particle) of the sulfide solid electrolyte material obtained in comparative example 4-1 ~ 4-4.
Embodiment
Below, the manufacture method of sulfide solid electrolyte material of the present invention, lithium battery and sulfide solid electrolyte material is described in detail.
A. sulfide solid electrolyte material
First, sulfide solid electrolyte material of the present invention is described.Sulfide solid electrolyte material of the present invention can be roughly divided into two execution modes.Below, for sulfide solid electrolyte material of the present invention, the first execution mode and the second execution mode is divided into be described.
1. the first execution mode
First, the first execution mode of sulfide solid electrolyte material of the present invention is described.The sulfide solid electrolyte material of the first execution mode uses containing Li 2the sulfide solid electrolyte material of the feedstock composition of the sulfide of S and IV main group or V major element, is characterized in that, in fact not containing crosslinked sulphur and Li 2s.
According to the present embodiment, sulfide solid electrolyte material is not owing to containing crosslinked sulphur and Li in fact 2s, therefore, it is possible to obtain the few sulfide solid electrolyte material of hydrogen sulfide generation.Such sulfide solid electrolyte material, has and just forms or its approximate composition, therefore, think that its stability for water is high, and hydrogen sulfide generation is low.At this, just generally refer to the oxyacid that hydrauture is the highest in the oxyacid identical oxide hydration obtained.In the present invention, by addition Li in sulfide 2the crystallization composition that S is maximum is called and just forms.Such as, Li 2s-P 2s 5li in system 3pS 4be equivalent to just form, Li 2s-SiS 2li in system 4siS 4be equivalent to just form, Li 2s-GeS 2li in system 4geS 4be equivalent to just form.Such as, at Li 2s-P 2s 5when being sulfide solid electrolyte material, the Li just formed 2the molar percentage of S is 75%.On the other hand, at Li 2s-SiS 2system or Li 2s-GeS 2when being sulfide solid electrolyte material, the Li just formed 2the molar percentage of S is 66.7%.
In addition, as mentioned above, Patent Document 1 discloses the 0.6Li utilizing melting and sharp cooling to manufacture 2s-0.4SiS 2be sulfide solid electrolyte material, 0.6Li 2s-0.4GeS 2it is sulfide solid electrolyte material etc.In addition, Patent Document 2 discloses the 60Li utilizing melting and sharp cooling to manufacture 2s-40SiS 2be sulfide solid electrolyte material, 63Li 2s-36SiS 2-1Li 3pO 4it is sulfide solid electrolyte material etc.But because these sulfide solid electrolyte materials have crosslinked sulphur, therefore, easy and water reacts, thus has the problem easily producing hydrogen sulfide.In contrast, the sulfide solid electrolyte material of the first execution mode does not have crosslinked sulphur in fact, therefore, it is possible to reduce hydrogen sulfide generation.
In addition, one of the feature of the sulfide solid electrolyte material of the first execution mode is " in fact containing crosslinked sulphur and Li 2s ".Wherein, " crosslinked sulphur " refers at Li 2crosslinked sulphur in the compound that the sulfide of S and IV main group or V major element reacts.Such as, Li is equivalent to 2s and P 2s 5the S of reaction 3p-S-PS 3crosslinked sulphur.Crosslinked Sulfur capacity so easily and water react, thus easily produce hydrogen sulfide.In the present invention, the Li in feedstock composition 2when the ratio of S is too small, sulfide solid electrolyte material can be caused to contain crosslinked sulphur.In addition, " in fact not containing crosslinked sulphur " can be confirmed by the mensuration of Raman spectrum.
Such as, at Li 2s-P 2s 5when being sulfide solid electrolyte material, preferably there is not S 3p-S-PS 3peak.S 3p-S-PS 3peak usually at 402cm -1place occurs.Therefore, in the present invention, preferably this peak do not detected.In addition, PS 4peak usually at 417cm -1place occurs.In the present invention, 402cm -1the intensity I at place 402preferably than 417cm -1the intensity I at place 417little.More specifically, relative to intensity I 417, intensity I 402such as be preferably less than 70%, be more preferably less than 50%, more preferably less than 35%.
On the other hand, " in fact not containing Li 2s " refer in fact not containing the Li from initiation material 2s.Li 2s easily and water react, thus easily produce hydrogen sulfide.In the present invention, Li in feedstock composition 2when the ratio of S becomes excessive, sulfide solid electrolyte material can be caused to contain Li 2s.In addition, " in fact not containing Li 2s " can be confirmed by X-ray diffraction.Specifically, not there is Li 2when the peak of S (2 θ=27.0 °, 31.2 °, 44.8 °, 53.1 °), can be judged as in fact not containing Li 2s.
(1) feedstock composition
First, the feedstock composition of the sulfide solid electrolyte material for the first execution mode is described.Feedstock composition in first execution mode, containing Li 2the sulfide of S and IV main group or V major element.In addition, feedstock composition also can contain other compounds.
The Li contained in feedstock composition 2s, preferred impurity is few.This is because can side reaction be suppressed.As Li 2the synthetic method of S, can enumerate the method etc. recorded in such as Japanese Unexamined Patent Publication 7-330312 publication.In addition, Li 2s preferably uses the method etc. recorded in WO2005/040039 to carry out purifying.
In addition, feedstock composition contains the sulfide of IV main group or V major element.As IV main group or V major element, there is no particular limitation, can enumerate such as Si, P and Ge etc., wherein, and preferred P.This is because, the low and sulfide solid electrolyte material that Li ionic conductivity is high of hydrogen sulfide generation can be obtained.As the sulfide of IV main group or V major element, specifically, can enumerate: P 2s 3, P 2s 5, SiS 2, GeS 2, As 2s 3, Sb 2s 3deng.In addition, feedstock composition also can contain multiple above-mentioned sulfide.
In addition, feedstock composition is except Li 2outside the sulfide of S and IV main group or V major element, can also containing being selected from Li 3pO 4, Li 4siO 4, Li 4geO 4, Li 3bO 3and Li 3alO 3in the positive oxyacid lithium of at least one.By adding so positive oxyacid lithium, more stable sulfide solid electrolyte material can be obtained.
In addition, in the first embodiment, feedstock composition is preferably at least containing Li 2s and P 2s 5, more preferably only containing Li 2s and P 2s 5.This is because, the low and sulfide solid electrolyte material that Li ionic conductivity is high of hydrogen sulfide generation can be obtained.In this situation, the Li contained in feedstock composition 2the molar percentage of S, as long as can obtain in fact not containing crosslinked sulphur and Li 2the ratio of the sulfide solid electrolyte material of S, then there is no particular limitation, such as, in the scope of 70% ~ 85%, wherein, preferably in the scope of 70% ~ 80%, particularly preferably in the scope of 72% ~ 78%.This is because, pass through Li 2the range set of the molar percentage of S is the scope comprising value (75%) and the approximation thereof just formed, and can reduce hydrogen sulfide generation further.
In addition, in the first embodiment, feedstock composition is preferably at least containing Li 2s and SiS 2, more preferably only containing Li 2s and SiS 2.Similarly, feedstock composition is preferably at least containing Li 2s and GeS 2, more preferably only containing Li 2s and GeS 2.This is because, the low and sulfide solid electrolyte material that Li ionic conductivity is high of hydrogen sulfide generation can be obtained.In these situations, the Li contained in feedstock composition 2the molar percentage of S, as long as can obtain in fact not containing crosslinked sulphur and Li 2the ratio of the sulfide solid electrolyte material of S, then there is no particular limitation, such as, in the scope of 50% ~ 80%, wherein, preferably in the scope of 55% ~ 75%, particularly preferably in the scope of 60% ~ 70%.This is because, pass through Li 2the range set of the molar percentage of S is the value (66.7%) and approximation thereof that are just being formed, can reduce hydrogen sulfide generation further.
(2) sulfide solid electrolyte material
The sulfide solid electrolyte material of the first execution mode, uses containing Li 2the feedstock composition of the sulfide of S and IV main group or V major element forms.Wherein, the sulfide solid electrolyte material of the first execution mode, preferably uses above-mentioned raw materials composition to be obtained by amorphization process.This is because, can obtain efficiently in fact not containing crosslinked sulphur and Li 2the sulfide solid electrolyte material of S.In addition, as amorphization process, can enumerate such as: mechanical milling method and melting and sharp cooling, wherein, preferred mechanical polishing.This is because, can process at normal temperatures, thus the simplification of manufacturing process can be realized.
The sulfide solid electrolyte material of the first execution mode, as long as in fact not containing crosslinked sulphur and Li 2s can be then chalcogenide glass, also can be the crystallization chalcogenide glass of being heat-treated by this chalcogenide glass and obtaining.Wherein, the sulfide solid electrolyte material of the first execution mode is preferably chalcogenide glass.This is presumably because, chalcogenide glass is more soft compared with crystallization chalcogenide glass, therefore, such as, when making solid state battery, can absorb the dilation of active material, cell excellent in cycle characteristics.In addition, chalcogenide glass, such as, can obtain by carrying out above-mentioned amorphization process to feedstock composition.On the other hand, crystallization chalcogenide glass, such as, can obtain by heat-treating chalcogenide glass.That is, by carrying out amorphization process and heat treatment successively to feedstock composition, crystallization chalcogenide glass can be obtained.It should be noted that, according to heat treated condition, to exist and generate crosslinked sulphur and Li 2the possibility of S and generate the possibility of metastable phase, therefore, in the present invention, preferably in the mode not generating these to regulate heat treatment temperature and heat treatment time.Crystallization chalcogenide glass particularly in the present invention, does not preferably have metastable phase.
In addition, the sulfide solid electrolyte material of the first execution mode, in predetermined hydrogen sulfide quantitative determination test, hydrogen sulfide generation from measuring in 300 seconds is preferably below 10cc/g, more preferably below 5cc/g, further preferred below 3cc/g, particularly preferably below 1cc/g.This is because, when hydrogen sulfide generation is few, the sulfide solid electrolyte material that fail safe is higher can be formed.Wherein, hydrogen sulfide quantitative determination test refers to following test.That is, in argon gas atmosphere, weigh sulfide solid electrolyte material 100mg, use and there is area for 1cm 2the granulating machine of forming section, at 5.1ton/cm 2pressure under this sample is pressurizeed, formed particle.Afterwards, obtained particle is configured in the inside of airtight drier (1755cc, air atmosphere, temperature 25 DEG C, humidity 40%), uses hydrogen sulfide sensor to be determined at the generation of the hydrogen sulfide produced in initial 300 seconds.
In addition, the sulfide solid electrolyte material of the first execution mode, the value of preferred Li ionic conductance is high.Li ionic conductance under normal temperature, such as, be preferably 10 -5more than S/cm, is more preferably 10 -4more than S/cm.In addition, the sulfide solid electrolyte material of the first execution mode is generally Powdered, and its average diameter is such as in the scope of 0.1 μm ~ 50 μm.In addition, as the purposes of sulfide solid electrolyte material, such as, can enumerate lithium battery purposes.Above-mentioned lithium battery can for having the all-solid lithium battery of solid electrolyte layer, also can for having the lithium battery of electrolyte.
2. the second execution mode
Below, the second execution mode of sulfide solid electrolyte material of the present invention is described.The sulfide solid electrolyte material of the second execution mode is by only containing Li 2s and P 2s 5feedstock composition amorphization and the sulfide solid electrolyte material obtained, it is characterized in that, the Li in above-mentioned raw materials composition 2the molar percentage of S is in the scope of 70% ~ 85%.
According to the present embodiment, by making the Li in feedstock composition 2the molar percentage of S, in predetermined scope, can form the sulfide solid electrolyte material that hydrogen sulfide generation is few.Such sulfide solid electrolyte material just forms or its approximate composition owing to having, and therefore, think that its stability for water is high, and hydrogen sulfide generation is low.It should be noted that, about the Li in feedstock composition 2the preferable range of the molar percentage of S, for the amorphization process of amorphization and other item, identical with the content recorded in above-mentioned " 1. the first execution mode ".
In addition, the present invention can provide a kind of sulfide solid electrolyte material, by only containing Li 2s and SiS 2feedstock composition amorphization and obtain, it is characterized in that, the Li in above-mentioned raw materials composition 2the molar percentage of S is in the scope of 50% ~ 80%.Similarly, the present invention can provide a kind of sulfide solid electrolyte material, by only containing Li 2s and GeS 2feedstock composition amorphization and obtain, it is characterized in that, the Li in above-mentioned raw materials composition 2the molar percentage of S is in the scope of 50% ~ 80%.About these sulfide solid electrolyte materials, think that, also due to reason similar to the above, hydrogen sulfide generation is low.It should be noted that, about the Li in feedstock composition 2the preferable range of the molar percentage of S, for the amorphization process of amorphization and other item, identical with the content recorded in above-mentioned " 1. the first execution mode ".
B. lithium battery
Below, lithium battery of the present invention is described.Lithium battery of the present invention, have: the positive electrode active material layer containing positive active material, negative electrode active material layer containing negative electrode active material and the dielectric substrate formed between described positive electrode active material layer and described negative electrode active material layer, it is characterized in that, at least one layer in described positive electrode active material layer, described negative electrode active material layer and described dielectric substrate is containing above-mentioned sulfide solid electrolyte material.
According to the present invention, by using above-mentioned sulfide solid electrolyte material, the lithium battery that hydrogen sulfide generation is few can be formed.
Fig. 1 is the schematic section of an example of the generating element representing lithium battery of the present invention.Generating element 10 shown in Fig. 1 has: the positive electrode active material layer 1 containing positive active material, the negative electrode active material layer 2 containing negative electrode active material and the dielectric substrate 3 formed between positive electrode active material layer 1 and negative electrode active material layer 2.In addition, the invention is characterized in, at least one layer in positive electrode active material layer 1, negative electrode active material layer 2 and dielectric substrate 3 states sulfide solid electrolyte material containing upper.
Below, each formation of lithium battery of the present invention is described.
1. dielectric substrate
First, the dielectric substrate in the present invention is described.Dielectric substrate in the present invention is the layer formed between positive electrode active material layer and negative electrode active material layer.As long as dielectric substrate can carry out the layer of the conduction of Li ion, then there is no particular limitation, the solid electrolyte layer be preferably made up of solid electrolyte material.This is because the high lithium battery of fail safe (all-solid-state battery) can be obtained.In addition, in the present invention, solid electrolyte layer is preferably containing above-mentioned sulfide solid electrolyte material.The ratio of the above-mentioned sulfide solid electrolyte material contained in solid electrolyte layer, such as, in the scope of 10 volume % ~ 100 volume %, wherein, preferably in the scope of 50 volume % ~ 100 volume %.In the present invention, particularly preferably solid electrolyte layer is only made up of above-mentioned sulfide solid electrolyte material.This is because the few lithium battery of hydrogen sulfide generation can be obtained.The thickness of solid electrolyte layer, such as, in the scope of 0.1 μm ~ 1000 μm, wherein, preferably in the scope of 0.1 μm ~ 300 μm.In addition, as the formation method of solid electrolyte layer, can enumerate such as: the method etc. of solid electrolyte material being carried out to compression molding.
In addition, the dielectric substrate in the present invention can be the layer be made up of electrolyte.By using electrolyte, the high lithium battery exported can be obtained.In this situation, at least one layer in usual positive electrode active material layer and negative electrode active material layer is containing above-mentioned sulfide solid electrolyte material.In addition, electrolyte is usually containing lithium salts and organic solvent (nonaqueous solvents).As lithium salts, can enumerate such as: LiPF 6, LiBF 4, LiClO 4, LiAsF 6deng inorganic lithium salt and LiCF 3sO 3, LiN (CF 3sO 2) 2, LiN (C 2f 5sO 2) 2, LiC (CF 3sO 2) 3deng organic lithium salt etc.As above-mentioned organic solvent, can enumerate such as: ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), butylene carbonate etc.
2. positive electrode active material layer
Below, the positive electrode active material layer in the present invention is described.Positive electrode active material layer in the present invention is the layer at least containing positive active material, as required, can also contain at least one in solid electrolyte material, conduction formed material and jointing material.Particularly in the present invention, the solid electrolyte material contained in positive electrode active material layer, is preferably above-mentioned sulfide solid electrolyte material.This is because the few lithium battery of hydrogen sulfide generation can be obtained.The ratio of the sulfide solid electrolyte material contained in positive electrode active material layer, different from the kind of lithium battery, such as in the scope of 0.1 volume % ~ 80 volume %, wherein, preferably in the scope of 1 volume % ~ 60 volume %, in the scope particularly preferably in 10 volume % ~ 50 volume %.In addition, as positive active material, can enumerate such as: LiCoO 2, LiMnO 2, Li 2niMn 3o 8, LiVO 2, LiCrO 2, LiFePO 4, LiCoPO 4, LiNiO 2, LiNi 1/3co 1/3mn 1/3o 2deng.
Positive electrode active material layer in the present invention can also containing conduction formed material.By adding conduction formed material, the conductivity of positive electrode active material layer can be made to improve.As conduction formed material, can enumerate such as: acetylene black, Ketjen black, carbon fiber etc.In addition, positive electrode active material layer also can contain jointing material.As the kind of jointing material, such as fluorine-containing jointing material etc. can be enumerated.In addition, the thickness of positive electrode active material layer is preferably in the scope of such as 0.1 μm ~ 1000 μm.
3. negative electrode active material layer
Below, the negative electrode active material layer in the present invention is described.Negative electrode active material layer in the present invention is the layer at least containing negative electrode active material, as required, can also contain at least one in solid electrolyte material, conduction formed material and jointing material.Particularly in the present invention, the solid electrolyte material contained in negative electrode active material layer, is preferably above-mentioned sulfide solid electrolyte material.This is because the few lithium battery of hydrogen sulfide generation can be obtained.The ratio of the sulfide solid electrolyte material contained in negative electrode active material layer, different from the kind of lithium battery, such as in the scope of 0.1 volume % ~ 80 volume %, wherein, preferably in the scope of 1 volume % ~ 60 volume %, in the scope particularly preferably in 10 volume % ~ 50 volume %.In addition, as negative electrode active material, such as metal active material and carbon active material can be enumerated.As metal active material, such as In, Al, Si and Sn etc. can be enumerated.On the other hand, as carbon active material, such as carbonaceous mesophase spherules (MCMB), high orientation graphite (HOPG), hard carbon, soft carbon etc. can be enumerated.It should be noted that, about for negative electrode active material layer solid electrolyte material and conduction formed material, identical with the situation of above-mentioned positive electrode active material layer.In addition, the thickness of negative electrode active material layer is such as in the scope of 0.1 μm ~ 1000 μm.
4. other are formed
Lithium battery of the present invention at least has above-mentioned positive electrode active material layer, dielectric substrate and negative electrode active material layer.Usually also have: the negative electrode collector of the positive electrode collector carrying out the current collection of positive electrode active material layer and the current collection carrying out negative electrode active material.As the material of positive electrode collector, such as SUS, aluminium, nickel, iron, titanium and carbon etc. can be enumerated, wherein, preferred SUS.On the other hand, as the material of negative electrode collector, such as SUS, copper, nickel and carbon etc. can be enumerated, wherein, preferred SUS.In addition, about the thickness and shape etc. of positive electrode collector and negative electrode collector, preferably suitably select according to the purposes etc. of lithium battery.In addition, the battery case used in the present invention, can use the battery case of common lithium battery.As battery case, such as SUS made cell box etc. can be enumerated.In addition, when lithium battery of the present invention is all-solid-state battery, generating element can be formed in the inside of dead ring.
5. lithium battery
Lithium battery of the present invention can be primary cell, also can be secondary cell, wherein, and preferred secondary cell.This is because, repeatedly charging and discharging can be carried out, such as useful as vehicle battery.As the shape of lithium battery of the present invention, can enumerate such as: Coin shape, cascade type, cylinder type and square etc.
In addition, the manufacture method of lithium battery of the present invention, as long as the method that can obtain above-mentioned lithium battery, then there is no particular limitation, can use the method same with the manufacture method of common lithium battery.Such as, when lithium battery of the present invention is all-solid-state battery, as an example of its manufacture method, method etc. can be listed below: by pressurizeing to the material forming the material of positive electrode active material layer, the material forming solid electrolyte layer and formation negative electrode active material layer successively, make generating element, this generating element is accommodated in the inside of battery case, and battery case is sealed.In addition, the present invention also can provide respectively be feature containing above-mentioned sulfide solid electrolyte positive electrode active material layer, negative electrode active material layer and solid electrolyte layer.
C. the manufacture method of sulfide solid electrolyte material
Below, the manufacture method of sulfide solid electrolyte material of the present invention is described.The feature of the manufacture method of sulfide solid electrolyte material of the present invention is to have: preparation section, and preparation is containing Li 2the feedstock composition of S and the sulfide containing IV main group or V major element; With amorphization operation, make described feedstock composition amorphization by amorphization process, and described feedstock composition is can obtain in fact not containing crosslinked sulphur and Li 2the ratio of the sulfide solid electrolyte material of S, containing described Li 2s and the sulfide containing IV main group or V major element.
According to the present invention, feedstock composition contains Li with predetermined ratio 2s and the sulfide containing IV main group or V major element, therefore, it is possible to obtain the few sulfide solid electrolyte material of hydrogen sulfide generation.
Fig. 2 is the key diagram of an example of the manufacture method that sulfide solid electrolyte material of the present invention is described.In manufacture method shown in Fig. 2, first, lithium sulfide (Li is prepared 2and phosphoric sulfide (P S) 2s 5) as initiation material.Then, these initiation materials are mixed, makes Li 2the molar percentage of S reaches 75%, thus raw materials composition (preparation section).Then, feedstock composition and grinding ball are put in tank, tank is airtight.Then, this tank is installed on planetary ball mill, makes feedstock composition amorphization (amorphization operation).Thus, obtained in fact not containing crosslinked sulphur and Li by feedstock composition 2the sulfide solid electrolyte material of S.
Below, each operation of the manufacture method of sulfide solid electrolyte material of the present invention is described.It should be noted that, in the present invention, (such as under Ar gas atmosphere) carries out each operation described later preferably under inert gas atmosphere.
1. preparation section
Preparation section in the present invention is that preparation is containing Li 2the operation of S and the feedstock composition containing the sulfide of IV main group or V major element.In addition, feedstock composition is can obtain in fact not containing crosslinked sulphur and Li 2the ratio of the sulfide solid electrolyte material of S, containing Li 2s and the sulfide containing IV main group or V major element.It should be noted that, about the feedstock composition used in the present invention, identical with the content recorded in above-mentioned " A. sulfide solid electrolyte material ", therefore, omit record herein.In addition, the preferred each uniform composition ground of feedstock composition disperses.
2. amorphization operation
Amorphization operation in the present invention is the operation being made above-mentioned raw materials composition amorphization by amorphization process.Thus, usually chalcogenide glass can be obtained.As amorphization process, such as mechanical milling method and melting and sharp cooling can be enumerated, wherein, preferred mechanical polishing.This is because, can process at normal temperatures, thus the simplification of manufacturing process can be realized.
As long as the method that mechanical lapping mixes while giving mechanical energy to feedstock composition, then there is no particular limitation, can enumerate such as ball milling, turbine grinding, mechanical fusion (mechanofusion), mill etc., wherein, preferred ball milling, particularly preferably planetary type ball-milling.This is because desired sulfide solid electrolyte material can be obtained efficiently.
In addition, the various conditions of mechanical lapping are preferably set to and can obtain in fact not containing crosslinked sulphur and Li 2the degree of the sulfide solid electrolyte material of S.Such as, when by planetary type ball-milling synthesizing sulfide solid electrolyte material, in tank, add feedstock composition and grinding ball, process with predetermined rotating speed and time.Usually, rotating speed is larger, and the formation speed of sulfide solid electrolyte material is faster, and the processing time is longer, higher to the conversion ratio of sulfide solid electrolyte material from feedstock composition.As rotating speed when carrying out planetary type ball-milling, such as, in the scope of 200rpm ~ 500rpm, wherein, preferably in the scope of 250rpm ~ 400rpm.In addition, carry out processing time during planetary type ball-milling, such as, in the scope of 1 hour ~ 100 hours, wherein, preferably in the scope of 1 hour ~ 50 hours.
3. heat treatment step
In the present invention, also can carry out the heat treatment step that the chalcogenide glass obtained by amorphization operation is heat-treated.Thus, usually crystallization chalcogenide glass can be obtained.It should be noted that, according to heat treated condition, to exist and generate crosslinked sulphur and Li 2the possibility of S and the possibility of generation metastable phase, therefore, in the present invention, preferably regulate heat treatment temperature and heat treatment time to make not generate these.
4. other
About the sulfide solid electrolyte material obtained by the present invention, identical with the content recorded in above-mentioned " A. sulfide solid electrolyte material ", therefore, omit record herein.In addition, the present invention can provide a kind of sulfide solid electrolyte material, it is characterized in that, is obtained by above-mentioned preparation section and amorphization operation.Similarly, the present invention can provide a kind of sulfide solid electrolyte material, it is characterized in that, is obtained by above-mentioned preparation section, amorphization operation and heat treatment step.
It should be noted that, the present invention is not limited to above-mentioned execution mode.Above-mentioned execution mode, for illustrating, has in fact identical formation with the technological thought recorded in the scope that request of the present invention is protected and the mode playing same action effect is also included in technical scope of the present invention.
Embodiment
Below illustrate that embodiment is more specifically described the present invention.
[embodiment 1-1 ~ 1-3]
As initiation material, use lithium sulfide (Li 2and phosphoric sulfide (P S) 2s 5).In glove box under an argon atmosphere, with for xLi 2s (100-x) P 2s 5the composition mode that reaches the mol ratio of x=70 weigh these powder, mix in agate mortar, obtain feedstock composition.Then, obtained feedstock composition 1g is dropped in the zirconia tank of 45ml, then drop into zirconia ball (Φ 10mm, 10), tank is completely airtight.This tank is installed on planetary ball mill, carries out the mechanical lapping of 40 hours with rotating speed 370rpm, obtain sulfide solid electrolyte material (embodiment 1-1).In addition, except making xLi 2s (100-x) P 2s 5composition in x value be changing into beyond x=75,80 respectively, to operate equally with embodiment 1-1, obtain sulfide solid electrolyte material (embodiment 1-2,1-3).
[comparative example 1-1 ~ 1-4]
Except making xLi 2s (100-x) P 2s 5composition in x value be changing into beyond x=0,50,66.7,100 respectively, to operate equally with embodiment 1-1, obtain sulfide solid electrolyte material.
[comparative example 1-5]
By the sulfide solid electrolyte material (x=70) obtained in embodiment 1-1 further in argon gas atmosphere, carry out heat treatment in 2 hours at 290 DEG C, thus, obtain the sulfide solid electrolyte material be made up of crystallization chalcogenide glass.
[evaluating 1]
(raman spectroscopy)
Use the sulfide solid electrolyte material obtained in embodiment 1-1 ~ 1-3, comparative example 1-2,1-3, carry out raman spectroscopy.The results are shown in Fig. 3.As shown in Figure 3, in comparative example 1-2 (x=50) and comparative example 1-3 (x=66.7), at 417cm -1near confirm the P with crosslinked sulphur 2s 7(S 3p-S-PS 3) peak.On the other hand, in embodiment 1-1 (x=70), embodiment 1-2 (x=75) and embodiment 1-3 (x=80), intensity I 402/ intensity I 417be respectively 65%, 30% and 14%.Thus, the sulfide solid electrolyte material confirming to obtain in embodiment 1-1 ~ 1-3 does not have crosslinked sulphur in fact.
(X-ray diffraction mensuration)
Use the sulfide solid electrolyte material obtained in embodiment 1-1,1-2, comparative example 1-2,1-4, carry out X-ray diffraction mensuration.The results are shown in Fig. 4.As shown in Figure 4, Li is observed in comparative example 1-4 (x=100) 2the peak of S, does not observe Li in embodiment 1-1,1-2, comparative example 1-2 2the peak of S.Thus, the sulfide solid electrolyte material confirming to obtain in embodiment 1-1,1-2, comparative example 1-2 is not in fact containing Li 2s.
(mensuration as the sulfide generation of particle)
Weigh the sulfide solid electrolyte material 100mg obtained in embodiment 1-1 ~ 1-3, comparative example 1-1 ~ 1-4 respectively, use and there is area for 1cm 2the granulating machine of forming section, at 5.1ton/cm 2pressure under these samples are pressurizeed, formed particle.Afterwards, obtained particle is placed on the inside of airtight drier (1755cc, air atmosphere, temperature 25 DEG C, humidity 40%), uses hydrogen sulfide sensor to be determined at the hydrogen sulfide generation produced in initial 300 seconds.These results are shown in Fig. 5.
As shown in Figure 5, confirm embodiment 1-1 ~ 1-3 compared with comparative example 1-1 ~ 1-4, hydrogen sulfide generation is low.Particularly when the value just formed (x=75), hydrogen sulfide generation demonstrates minimum value (0.2cc/g).
(mensuration as the sulfide generation of battery)
Use the sulfide solid electrolyte material obtained in embodiment 1-2 and comparative example 1-5, make all-solid lithium battery respectively.It should be noted that, the making of battery is all carried out in argon gas atmosphere.First, use granulating machine at 1ton/cm 2pressure under sulfide solid electrolyte material (51mg) is pressurizeed, formed solid electrolyte layer.Then, the surface of solid electrolyte layer is added by LiCoO 2(8.9mg) and the anode mixture that forms of above-mentioned sulfide solid electrolyte material (3.8mg), use granulating machine at 1ton/cm 2pressure under pressurize, formed positive electrode active material layer.Then, the surface of solid electrolyte layer not forming positive electrode active material layer is added the cathode agent be made up of graphite (4.71mg) and above-mentioned sulfide solid electrolyte material (4.71mg), uses granulating machine at 4.3ton/cm 2pressure under pressurize, formed negative electrode active material layer.Obtain generating element thus.Clamp this generating element with collector body SUS, make all-solid lithium battery.
Obtained all-solid lithium battery is configured in the inside of airtight drier (1755cc, air atmosphere, temperature 25 DEG C, humidity 40%), uses hydrogen sulfide sensor to measure the change of hydrogen sulfide generation relative to open-assembly time in air.These results are shown in Fig. 6.As shown in Figure 6, in comparative example 1-5, hydrogen sulfide generation through time increase, the hydrogen sulfide generation through 150 seconds time is 0.056cc.In contrast, in embodiment 1-2, have no hydrogen sulfide generation through time increase, the hydrogen sulfide generation through 150 seconds time is below 0.001cc.
[embodiment 2-1,2-2]
As initiation material, use lithium sulfide (Li 2and silicon sulfide (SiS S) 2).In glove box under an argon atmosphere, with for xLi 2s (100-x) SiS 2the composition mode that reaches the mol ratio of x=50 weigh these powder, mix in agate mortar, obtain feedstock composition.Except using this feedstock composition, to operate equally with embodiment 1-1, obtain sulfide solid electrolyte material (embodiment 2-1).In addition, except making xLi 2s (100-x) SiS 2composition in x value be changing into beyond x=66.7, to operate equally with embodiment 2-1, obtain sulfide solid electrolyte material (embodiment 2-2).
[comparative example 2-1,2-2]
Except making xLi 2s (100-x) SiS 2composition in x value be changing into beyond x=0,100 respectively, to operate equally with embodiment 2-1, obtain sulfide solid electrolyte material.
[embodiment 3-1 ~ 3-3]
As initiation material, use lithium sulfide (Li 2and germanium sulfide (GeS S) 2).In glove box under an argon atmosphere, with for xLi 2s (100-x) GeS 2the composition mode that reaches the mol ratio of x=50 weigh these powder, mix in agate mortar, obtain feedstock composition.Except using this feedstock composition, to operate equally with embodiment 1-1, obtain sulfide solid electrolyte material (embodiment 3-1).In addition, except making xLi 2s (100-x) GeS 2composition in x value be changing into beyond x=66.7,75 respectively, to operate equally with embodiment 3-1, obtain sulfide solid electrolyte material (embodiment 3-2,3-3).
[comparative example 3-1,3-2]
Except making xLi 2s (100-x) GeS 2composition in x value be changing into beyond x=0,100 respectively, to operate equally with embodiment 3-1, obtain sulfide solid electrolyte material.
[comparative example 4-1 ~ 4-4]
As initiation material, use lithium sulfide (Li 2and aluminium sulfide (Al S) 2s 3).In glove box under an argon atmosphere, with for xLi 2s (100-x) Al 2s 3composition reach x=0,50,75, the mode of the mol ratio of 100 weighs these powder, mix in agate mortar, obtain feedstock composition.Except using these feedstock compositions, to operate equally with embodiment 1-1, obtain sulfide solid electrolyte material.
[evaluating 2]
(mensuration as the sulfide generation of particle)
Use the sulfide solid electrolyte material obtained in embodiment 2-1,2-2, comparative example 2-1,2-2, embodiment 3-1 ~ 3-3, comparative example 3-1,3-2, comparative example 4-1 ~ 4-4, carry out the mensuration of the sulfide generation as particle.It should be noted that, the manufacture method of particle and the assay method of hydrogen sulfide generation same as described above.These results are shown in Fig. 7 ~ Fig. 9.As shown in Figure 7, confirm embodiment 2-1,2-2 compared with comparative example 2-1,2-2, hydrogen sulfide generation is low.Particularly for the value just formed (x=66.7), hydrogen sulfide generation demonstrates minimum value.Similarly, as shown in Figure 8, confirm embodiment 3-1 ~ 3-3 compared with comparative example 3-2, hydrogen sulfide generation is low.Particularly for the value just formed (x=66.7), hydrogen sulfide generation demonstrates minimum value.It should be noted that, comparative example 3-1, due to not containing Li, so there is no demonstrate Li ionic conductivity.On the other hand, as shown in Figure 9, in comparative example 4-1 ~ 4-4, hydrogen sulfide generation all increases.Confirming thus, when the sulfide solid electrolyte material of use III major element Al, not having to demonstrate minimum when just forming as using the sulfide solid electrolyte material of IV major element Si and Ge, V major element P.In addition, use the sulfide solid electrolyte material obtained in embodiment 2-1,2-2,3-1 ~ 3-3, measure the sulfide generation as battery, result all can not make hydrogen sulfide generation reduce.
Label declaration
1 ... positive electrode active material layer
2 ... negative electrode active material layer
3 ... dielectric substrate
10 ... generating element

Claims (4)

1. a sulfide solid electrolyte material, containing Li 3pS 4, it is characterized in that,
Measured by X-ray diffraction and Li do not detected 2the peak of S,
402cm in raman spectroscopy -1intensity relative to 417cm -1intensity I 417be less than 35%,
Use has area for 1cm 2the granulating machine of forming section, at 5.1ton/cm 2pressure under described sulfide solid electrolyte material 100mg is pressurizeed, form particle, described particle is placed on the inside of airtight drier, and when using hydrogen sulfide sensor to be determined at the hydrogen sulfide generation produced in initial 300 seconds, described hydrogen sulfide generation is below 1cc/g, wherein, the condition of described drier is 1755cc, air atmosphere, temperature 25 DEG C, humidity 40%.
2. sulfide solid electrolyte material as claimed in claim 1, is characterized in that, uses containing Li 2s and P 2s 5feedstock composition form.
3. sulfide solid electrolyte material as claimed in claim 1 or 2, it is characterized in that, described sulfide solid electrolyte material is chalcogenide glass.
4. a lithium battery, has: the positive electrode active material layer containing positive active material, negative electrode active material layer containing negative electrode active material and the dielectric substrate formed between described positive electrode active material layer and described negative electrode active material layer, is characterized in that,
At least one layer in described positive electrode active material layer, described negative electrode active material layer and described dielectric substrate is containing the sulfide solid electrolyte material according to any one of claims 1 to 3.
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